WO2012164914A1 - Copolymère, composition de caoutchouc, composition de caoutchouc réticulée, et pneu - Google Patents

Copolymère, composition de caoutchouc, composition de caoutchouc réticulée, et pneu Download PDF

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Publication number
WO2012164914A1
WO2012164914A1 PCT/JP2012/003507 JP2012003507W WO2012164914A1 WO 2012164914 A1 WO2012164914 A1 WO 2012164914A1 JP 2012003507 W JP2012003507 W JP 2012003507W WO 2012164914 A1 WO2012164914 A1 WO 2012164914A1
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group
copolymer
rubber composition
conjugated diene
diene compound
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PCT/JP2012/003507
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English (en)
Japanese (ja)
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堀川　泰郎
会田　昭二郎
オリビエ タルディフ
純子 松下
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株式会社ブリヂストン
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Priority to BR112013030818A priority Critical patent/BR112013030818A2/pt
Priority to CN201280026894.0A priority patent/CN103562246B/zh
Priority to RU2013156826/04A priority patent/RU2553474C1/ru
Priority to JP2013517875A priority patent/JP5739991B2/ja
Priority to EP12793513.8A priority patent/EP2716670B1/fr
Priority to US14/119,915 priority patent/US9139680B2/en
Publication of WO2012164914A1 publication Critical patent/WO2012164914A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
    • C08F297/086—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene the block polymer contains at least three blocks
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a copolymer of a conjugated diene compound and a non-conjugated olefin, a rubber composition, a crosslinked rubber composition, and a tire, and in particular, produces a rubber having excellent fatigue resistance, low heat buildup, and fracture elongation.
  • a block copolymer comprising a conjugated diene compound and a non-conjugated olefin, a rubber composition containing the block copolymer, a crosslinked rubber composition obtained by crosslinking the rubber composition, and the above
  • the present invention relates to a rubber composition or a tire using the crosslinked rubber composition.
  • Patent Document 1 discloses a conjugated diene polymerization catalyst containing a Group IV transition metal compound having a cyclopentadiene ring structure, which is co-polymerized with the conjugated diene.
  • the polymerizable monomer include ⁇ -olefins such as ethylene, but there is no mention of the arrangement of monomer units in the copolymer.
  • Patent Document 2 discloses a copolymer of an ⁇ -olefin and a conjugated diene compound, but the arrangement of monomer units in the copolymer is completely different. Not mentioned.
  • Patent Document 3 discloses a copolymer of ethylene and butadiene synthesized using a special organometallic complex as a catalyst component. Is inserted into the copolymer in the form of trans-1,2-cyclohexane, and the arrangement of the monomer units in the copolymer is not mentioned at all, and the conjugated diene is not mentioned at all.
  • the length of the non-conjugated olefin-derived portion (molecular weight) in the block copolymer of the compound and the non-conjugated olefin a rubber excellent in fatigue resistance, low heat build-up, and fracture elongation is produced. There is no description about this.
  • JP-A-11-228743 discloses an unsaturated elastomer composition comprising an unsaturated olefin copolymer and rubber, but the monomer in the copolymer.
  • the unit arrangement is only described as random, and the length (molecular weight) of the non-conjugated olefin-derived part in the block copolymer of the conjugated diene compound and the non-conjugated olefin is specified.
  • Patent Document 5 discloses that the vinyl content (vinyl bond content, 1,2-adduct (including 3,4-adduct) content) is 6%, and the cis content. A butadiene polymer with a% of 92% and an ethylene content of 3% or 9% is disclosed. However, since the ethylene-derived part of the copolymer is long (molecular weight is large), based on the crystallinity of ethylene, the physical properties of the copolymer are close to those of plastics, fatigue resistance (flexion, elongation test) and elongation at break There is a problem that gets worse.
  • JP-A-2000-86857 defines the length (molecular weight) of a non-conjugated olefin-derived portion in a block copolymer of a conjugated diene compound and a non-conjugated olefin. There is no description or suggestion of producing a rubber excellent in fatigue resistance, low heat build-up, and breaking elongation.
  • an object of the present invention is to produce a block copolymer comprising a conjugated diene compound and a non-conjugated olefin, which is used to produce a rubber having excellent fatigue resistance, low heat build-up, and fracture elongation.
  • the object is to provide a rubber composition containing a coalescence, a crosslinked rubber composition obtained by crosslinking the rubber composition, and a tire using the rubber composition or the crosslinked rubber composition.
  • the length of the block part (molecular weight) consisting of the monomer units of the non-conjugated olefin is regulated. It has been found that a rubber excellent in fatigue, low heat build-up, and elongation at break can be produced, and the present invention has been completed.
  • the copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, and is a block copolymer.
  • DSC differential scanning calorimetry
  • the block copolymer means a copolymer composed of a block portion composed of monomer units of a conjugated diene compound and a block portion composed of monomer units of a non-conjugated olefin.
  • the cis-1,4 bond content of the conjugated diene compound-derived moiety is 80% or more.
  • the content of the non-conjugated olefin (part derived from the non-conjugated olefin) exceeds 0 mol% and is 40 mol% or less.
  • the structure of the block copolymer is (AB) x , A- (BA) x and B- (AB) x (where , A is a block portion consisting of a monomer unit of a non-conjugated olefin, B is a block portion consisting of a monomer unit of a conjugated diene compound, and x is an integer of 1 or more) is there.
  • a block copolymer having a plurality of (AB) or (BA) structures is referred to as a multi-block copolymer.
  • the copolymer of the present invention preferably has a polystyrene equivalent weight average molecular weight of 10,000 to 10,000,000.
  • the copolymer of the present invention preferably has a molecular weight distribution (Mw / Mn) of 10 or less.
  • the non-conjugated olefin is an acyclic olefin.
  • the non-conjugated olefin has 2 to 10 carbon atoms.
  • the non-conjugated olefin is preferably at least one selected from the group consisting of ethylene, propylene and 1-butene, more preferably ethylene.
  • the conjugated diene compound is at least one selected from the group consisting of 1,3-butadiene and isoprene.
  • the rubber composition of the present invention includes the copolymer of the present invention.
  • the rubber composition of the present invention preferably contains 5 to 200 parts by mass of a reinforcing filler and 0.1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the rubber component.
  • the crosslinked rubber composition of the present invention is obtained by crosslinking the rubber composition of the present invention.
  • the tire of the present invention is characterized by using the rubber composition of the present invention or the crosslinked rubber composition of the present invention.
  • a block copolymer comprising a conjugated diene compound and a non-conjugated olefin, which is used to produce a rubber having excellent fatigue resistance, low heat build-up, and excellent elongation at break
  • a rubber composition containing the rubber composition, a crosslinked rubber composition obtained by crosslinking the rubber composition, and a tire using the rubber composition or the crosslinked rubber composition can be provided.
  • the DSC curve of the block copolymer A is shown.
  • the DSC curve of the block copolymer B is shown.
  • the DSC curve of the block copolymer C is shown.
  • the DSC curve of the random copolymer D is shown.
  • the DSC curve of the block copolymer E is shown.
  • the DSC curve of the taper copolymer F is shown.
  • the copolymer of the present invention is a copolymer of a conjugated diene compound and a non-conjugated olefin, and is a block copolymer.
  • the differential scanning calorimetry (DSC) measurement according to JIS K 7121-1987 is 70 ° C.
  • the peak area at ⁇ 110 ° C. is 60% or more of the peak area at 40 ° C. to 140 ° C., and the peak area at 110 ° C. to 140 ° C. is 20% or less of the peak area at 40 ° C. to 140 ° C. .
  • the copolymer of the present invention has a block portion composed of a monomer unit of non-conjugated olefin, and exhibits static crystallinity, so that it has excellent mechanical properties such as breaking strength. Moreover, since the copolymer of this invention is provided with the block part which consists of a monomer unit of a conjugated diene compound, it becomes possible to act as an elastomer.
  • differential scanning calorimetry and nuclear magnetic resonance (NMR) are used as main measuring means for confirming the formation of the block copolymer.
  • the differential scanning calorimetry is a measurement method performed in accordance with JIS K 7121-1987. Specifically, by DSC, a glass transition temperature derived from a block portion composed of monomer units of a conjugated diene compound, a crystallization temperature derived from the block portion, and a block portion composed of monomer units of a non-conjugated olefin.
  • the peak area at 70 ° C. to 110 ° C. is 60% or more of the peak area at 40 ° C. to 140 ° C., and the peak at 110 ° C. to 140 ° C.
  • DSC differential scanning calorimetry
  • the peak at 110 ° C. to 140 ° C. indicates that a block portion composed of a monomer unit of a non-conjugated olefin (for example, ethylene) having a relatively small weight average molecular weight (about 1000 to about 30000) is formed
  • the peak at 110 ° C. to 140 ° C. indicates that a block portion composed of a monomer unit of a non-conjugated olefin (for example, ethylene) having a large weight average molecular weight (about 30000 or more) is formed.
  • the peak at 40 ° C. to 140 ° C. is a peak based on a portion derived from a non-conjugated olefin (for example, ethylene). Therefore, the peak area at 70 ° C.
  • the peak area at 110 ° C. to 140 ° C. is 60% or more of the peak area at 40 ° C. to 140 ° C.
  • the peak area at 110 ° C. to 140 ° C. is 20% or less of the peak area at 40 ° C. to 140 ° C.
  • the cis-1,4 bond amount of the conjugated diene compound portion is preferably 80% or more, more preferably more than 92%, particularly preferably 95% or more, 97% or more is most preferable. If the cis-1,4 bond amount of the conjugated diene compound portion (part derived from the conjugated diene compound) is 80% or more, the block portion consisting of the monomer unit of the conjugated diene compound exhibits elongation crystallinity, Mechanical properties such as fatigue resistance can be further improved.
  • the amount of the cis-1,4 bond is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
  • the content of 1,2-adduct (including 3,4-adduct) of the conjugated diene compound (including the 1,4-adduct of the conjugated diene compound in the conjugated diene compound-derived portion (3,4 addition)
  • the content) (including body part) is preferably 5% or less.
  • the copolymer of the present invention can further improve ozone resistance and fatigue resistance. it can.
  • the copolymer of the present invention has ozone resistance and fatigue resistance. Further improvement can be achieved.
  • the content of 1,2-adduct (including 3,4-adduct) in the conjugated diene compound portion is more preferably 2.0% or less.
  • the content of the 1,2 adduct portion (including the 3,4 adduct portion) is an amount in the portion derived from the conjugated diene compound, and is not a ratio to the whole copolymer.
  • the 1,2-adduct portion (including 3,4-adduct portion) content of the conjugated diene compound portion (including the 3,4-adduct portion) Including) content) has the same meaning as the amount of 1,2-vinyl bonds when the conjugated diene compound is butadiene.
  • the copolymer of the present invention does not cause a problem of lowering the molecular weight, and its weight average molecular weight (Mw) is not particularly limited, but from the viewpoint of application to a polymer structural material, the copolymer
  • the weight average molecular weight (Mw) in terms of polystyrene of the coalescence is preferably 10,000 to 10,000,000, more preferably 10,000 to 1,000,000, and further preferably 50,000 to 600,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 10 or less, and more preferably 5 or less. This is because if the molecular weight distribution exceeds 10, the physical properties are not uniform.
  • the average molecular weight and the molecular weight distribution can be determined using polystyrene as a standard substance by gel permeation chromatography (GPC).
  • the content of non-conjugated olefin is preferably more than 0 mol% and 40 mol% or less. If the content of the non-conjugated olefin (part derived from the non-conjugated olefin) is within the above specified range, mechanical properties such as breaking strength can be improved more reliably. In addition, from the viewpoint of improving mechanical properties such as breaking strength without causing phase separation of the copolymer, the content of the non-conjugated olefin (non-conjugated olefin-derived portion) exceeds 0 mol% and is 30 mol% or less. More preferably it is.
  • the content of the conjugated diene compound is preferably 60 mol% or more and less than 100 mol%, and more preferably 70 mol% or more and less than 100 mol%. preferable. If the content of the conjugated diene compound (part derived from the conjugated diene compound) is within the above specified range, the copolymer of the present invention can behave uniformly as an elastomer.
  • examples of the structure of the block copolymer include (AB) x , A- (BA) x , B- (AB) x and the like.
  • A is a block part composed of monomer units of non-conjugated olefin
  • B is a block part composed of monomer units of conjugated diene compound
  • x is an integer of 1 or more, preferably It is an integer from 1 to 5.
  • the boundaries between the block portions do not need to be clearly distinguished, for example, a portion made of a mixture of a conjugated diene compound and a non-conjugated olefin between the block portion A and the block portion B, a so-called tapered structure. May be formed.
  • the conjugated diene compound used as the monomer preferably has 4 to 12 carbon atoms.
  • Specific examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, and among these, 1,3-butadiene and isoprene are preferable.
  • these conjugated diene compounds may be used independently and may be used in combination of 2 or more type.
  • the copolymer of the present invention can be prepared by the same mechanism using any of the specific examples of the conjugated diene compound described above.
  • the non-conjugated olefin used as the monomer is a non-conjugated olefin other than the conjugated diene compound, and is preferably an acyclic olefin.
  • the non-conjugated olefin preferably has 2 to 10 carbon atoms.
  • preferred examples of the non-conjugated olefin include ⁇ -olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene and 1-octene. Among these, ethylene, propylene And 1-butene are more preferable, and ethylene is particularly preferable.
  • These non-conjugated olefins may be used alone or in combination of two or more.
  • the olefin refers to a compound that is an aliphatic unsaturated hydrocarbon and has one or more carbon-carbon double bonds.
  • the 1st manufacturing method of the copolymer of this invention includes the process of superposing
  • a polymerization method any method such as a solution polymerization method, a suspension polymerization method, a liquid phase bulk polymerization method, an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used.
  • a solvent for a polymerization reaction the solvent used should just be inactive in a polymerization reaction, For example, toluene, hexane, cyclohexane, mixtures thereof etc. are mentioned.
  • the polymerization catalyst composition includes the following general formula (I): (wherein M represents a lanthanoid element, scandium or yttrium, Cp R each independently represents an unsubstituted or substituted indenyl group, and R a to R f each independently represents an alkyl having 1 to 3 carbon atoms.
  • M represents a lanthanoid element, scandium or yttrium
  • Cp R each independently represents an unsubstituted or substituted indenyl group
  • X ′ represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group.
  • a silyl group or a hydrocarbon group having 1 to 20 carbon atoms L represents a neutral Lewis base, and w represents an integer of 0 to 3, and the following general formula (III ):
  • M represents a lanthanoid element, scandium or yttrium
  • Cp R ′ represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl
  • X represents a hydrogen atom, a halogen atom, an alkoxide group or a thiolate group.
  • a polymerization catalyst composition (hereinafter also referred to as a first polymerization catalyst composition) comprising at least one complex selected from the group consisting of a half metallocene cation complex represented by The product may further contain other components contained in the polymerization catalyst composition containing a normal metallocene complex, such as a promoter.
  • the metallocene complex is a complex compound in which one or more cyclopentadienyl or a derivative thereof is bonded to a central metal, and in particular, one cyclopentadienyl or a derivative thereof bonded to the central metal.
  • a certain metallocene complex may be called a half metallocene complex.
  • the concentration of the complex contained in the first polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.
  • Cp R in the formula is an unsubstituted indenyl or substituted indenyl.
  • Cp R having an indenyl ring as a basic skeleton can be represented by C 9 H 7-X R X or C 9 H 11-X R X.
  • X is an integer of 0 to 7 or 0 to 11.
  • each R is preferably independently a hydrocarbyl group or a metalloid group.
  • the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • hydrocarbyl group examples include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
  • metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
  • Specific examples of the metalloid group include a trimethylsilyl group.
  • substituted indenyl examples include 2-phenylindenyl, 2-methylindenyl and the like. Note that the two Cp Rs in the general formulas (I) and (II) may be the same as or different from each other.
  • Cp R ′ in the formula is unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl, and among these, unsubstituted or substituted indenyl It is preferable that Cp R ′ having a cyclopentadienyl ring as a basic skeleton is represented by C 5 H 5-X R X. Here, X is an integer of 0 to 5.
  • each R is preferably independently a hydrocarbyl group or a metalloid group.
  • the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
  • examples of metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
  • Specific examples of the metalloid group include a trimethylsilyl group.
  • Specific examples of Cp R ′ having a cyclopentadienyl ring as a basic skeleton include the following. (In the formula, R represents a hydrogen atom, a methyl group or an ethyl group.)
  • Cp R ′ having the above indenyl ring as a basic skeleton is defined in the same manner as Cp R in the general formula (I), and preferred examples thereof are also the same.
  • Cp R ′ having the fluorenyl ring as a basic skeleton can be represented by C 13 H 9-X R X or C 13 H 17-X R X.
  • X is an integer of 0 to 9 or 0 to 17.
  • each R is preferably independently a hydrocarbyl group or a metalloid group.
  • the hydrocarbyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • Specific examples of the hydrocarbyl group include a methyl group, an ethyl group, a phenyl group, and a benzyl group.
  • metalloid group metalloids include germyl Ge, stannyl Sn, and silyl Si, and the metalloid group preferably has a hydrocarbyl group, and the hydrocarbyl group that the metalloid group has is the same as the above hydrocarbyl group. is there.
  • Specific examples of the metalloid group include a trimethylsilyl group.
  • the central metal M in the general formulas (I), (II), and (III) is a lanthanoid element, scandium, or yttrium.
  • the lanthanoid elements include 15 elements having atomic numbers of 57 to 71, and any of these may be used.
  • Preferred examples of the central metal M include samarium Sm, neodymium Nd, praseodymium Pr, gadolinium Gd, cerium Ce, holmium Ho, scandium Sc, and yttrium Y.
  • the metallocene complex represented by the general formula (I) includes a silylamide ligand [—N (SiR 3 ) 2 ].
  • the R groups contained in the silylamide ligand (R a to R f in the general formula (I)) are each independently an alkyl group having 1 to 3 carbon atoms or a hydrogen atom.
  • R a to R f is a hydrogen atom.
  • the alkyl group is preferably a methyl group.
  • the metallocene complex represented by the general formula (II) contains a silyl ligand [—SiX ′ 3 ].
  • X ′ contained in the silyl ligand [—SiX ′ 3 ] is a group defined in the same manner as X in the general formula (III) described below, and preferred groups are also the same.
  • X is a group selected from the group consisting of a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, and a hydrocarbon group having 1 to 20 carbon atoms.
  • examples of the alkoxide group include aliphatic alkoxy groups such as methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group; phenoxy group, 2,6-dioxy -Tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6-isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, Examples include aryloxide groups such as 2-isopropyl-6-neopentylphenoxy group, and among these, 2,6-di-tert-butylphenoxy group is preferable.
  • the thiolate group represented by X includes a thiomethoxy group, a thioethoxy group, a thiopropoxy group, a thio n-butoxy group, a thioisobutoxy group, a thiosec-butoxy group, a thiotert-butoxy group and the like Group thiolate group; thiophenoxy group, 2,6-di-tert-butylthiophenoxy group, 2,6-diisopropylthiophenoxy group, 2,6-dineopentylthiophenoxy group, 2-tert-butyl-6-isopropyl Arylthiolate groups such as thiophenoxy group, 2-tert-butyl-6-thioneopentylphenoxy group, 2-isopropyl-6-thioneopentylphenoxy group, 2,4,6-triisopropylthiophenoxy group, etc. Among these, 2,4,6-triisopropylthiophenoxy group,
  • examples of the amide group represented by X include aliphatic amide groups such as dimethylamide group, diethylamide group, diisopropylamide group; phenylamide group, 2,6-di-tert-butylphenylamide group, 2 , 6-diisopropylphenylamide group, 2,6-dineopentylphenylamide group, 2-tert-butyl-6-isopropylphenylamide group, 2-tert-butyl-6-neopentylphenylamide group, 2-isopropyl- Arylamido groups such as 6-neopentylphenylamide group and 2,4,6-tri-tert-butylphenylamide group; bistrialkylsilylamide groups such as bistrimethylsilylamide group, among them bistrimethylsilylamide Groups are preferred.
  • examples of the silyl group represented by X include trimethylsilyl group, tris (trimethylsilyl) silyl group, bis (trimethylsilyl) methylsilyl group, trimethylsilyl (dimethyl) silyl group, triisopropylsilyl (bistrimethylsilyl) silyl group, and the like.
  • a tris (trimethylsilyl) silyl group is preferable.
  • the halogen atom represented by X may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, but a chlorine atom or a bromine atom is preferred.
  • Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by X include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • Linear or branched aliphatic hydrocarbon groups such as butyl group, neopentyl group, hexyl group, octyl group; aromatic hydrocarbon groups such as phenyl group, tolyl group, naphthyl group; aralkyl groups such as benzyl group, etc.
  • Others include hydrocarbon groups containing silicon atoms such as trimethylsilylmethyl group and bistrimethylsilylmethyl group. Among these, methyl group, ethyl group, isobutyl group, trimethylsilylmethyl group and the like are preferable.
  • X is preferably a bistrimethylsilylamide group or a hydrocarbon group having 1 to 20 carbon atoms.
  • the non-coordinating anion represented by, for example, a tetravalent boron anion.
  • tetravalent boron anion include tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dica
  • the metallocene complex represented by the above general formulas (I) and (II) and the half metallocene cation complex represented by the above general formula (III) are further 0 to 3, preferably 0 to 1 neutral.
  • examples of the neutral Lewis base L include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, neutral diolefins, and the like.
  • the neutral Lewis bases L may be the same or different.
  • metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the general formula (III) may exist as a monomer, It may exist as a body or higher multimer.
  • the metallocene complex represented by the general formula (I) includes, for example, a lanthanoid trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt) and bis (trialkylsilyl). It can be obtained by reacting with an amide salt (for example, potassium salt or lithium salt).
  • reaction temperature should just be about room temperature, it can manufacture on mild conditions.
  • the reaction time is arbitrary, but is about several hours to several tens of hours.
  • the reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used. Below, the reaction example for obtaining the metallocene complex represented by general formula (I) is shown. (In the formula, X ′′ represents a halide.)
  • the metallocene complex represented by the general formula (II) includes, for example, a lanthanide trishalide, scandium trishalide, or yttrium trishalide in a solvent, an indenyl salt (for example, potassium salt or lithium salt), and a silyl salt (for example, potassium). Salt or lithium salt).
  • reaction temperature should just be about room temperature, it can manufacture on mild conditions.
  • the reaction time is arbitrary, but is about several hours to several tens of hours.
  • the reaction solvent is not particularly limited, but is preferably a solvent that dissolves the raw material and the product. For example, toluene may be used.
  • the reaction example for obtaining the metallocene complex represented by general formula (II) is shown. (In the formula, X ′′ represents a halide.)
  • the half metallocene cation complex represented by the general formula (III) can be obtained, for example, by the following reaction.
  • M represents a lanthanoid element, scandium or yttrium, and Cp R ′ independently represents unsubstituted or substituted cyclopentadienyl, indenyl or fluorenyl.
  • X represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, or a hydrocarbon group having 1 to 20 carbon atoms
  • L represents a neutral Lewis base
  • w represents 0 to 3 Indicates an integer.
  • [A] + [B] ⁇ [A] + represents a cation
  • [B] ⁇ represents a non-coordinating anion.
  • Examples of the cation represented by + include a carbonium cation, an oxonium cation, an amine cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
  • Examples of the carbonium cation include trisubstituted carbonium cations such as a triphenylcarbonium cation and a tri (substituted phenyl) carbonium cation.
  • the tri (substituted phenyl) carbonyl cation is specifically exemplified by tri (methylphenyl). ) Carbonium cation and the like.
  • amine cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation; N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N— N, N-dialkylanilinium cations such as 2,4,6-pentamethylanilinium cation; dialkylammonium cations such as diisopropylammonium cation and dicyclohexylammonium cation.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation
  • Examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • N, N-dialkylanilinium cation or carbonium cation is preferable, and N, N-dialkylanilinium cation is particularly preferable.
  • the ionic compound represented by the general formula [A] + [B] ⁇ used in the above reaction is a compound selected and combined from the above non-coordinating anions and cations, and is an N, N-dimethylaniline. Preference is given to nium tetrakis (pentafluorophenyl) borate, triphenylcarbonium tetrakis (pentafluorophenyl) borate and the like.
  • general formula [A] + [B] - ionic compounds represented by is preferably added from 0.1 to 10 mols per mol of the metallocene complex, more preferably added about 1 molar.
  • the half metallocene cation complex represented by the general formula (III) may be provided as it is in the polymerization reaction system, or the compound represented by the general formula (IV) and the general formula used in the reaction [a] + [B] - provides an ionic compound represented separately into the polymerization reaction system, the general formula in the reaction system (III You may form the half metallocene cation complex represented by this.
  • the structures of the metallocene complex represented by the general formulas (I) and (II) and the half metallocene cation complex represented by the general formula (III) are preferably determined by X-ray structural analysis.
  • the co-catalyst that can be used in the first polymerization catalyst composition can be arbitrarily selected from components used as a co-catalyst for a polymerization catalyst composition containing a normal metallocene complex.
  • suitable examples of the cocatalyst include aluminoxanes, organoaluminum compounds, and the above ionic compounds. These promoters may be used alone or in combination of two or more.
  • the aluminoxane is preferably an alkylaminoxan, and examples thereof include methylaluminoxane (MAO) and modified methylaluminoxane. Further, as the modified methylaluminoxane, MMAO-3A (manufactured by Tosoh Finechem) and the like are preferable.
  • the content of aluminoxane in the first polymerization catalyst composition is such that the element ratio Al / M between the central metal M of the metallocene complex and the aluminum element Al of the aluminoxane is about 10 to 1000, preferably about 100. It is preferable to make it.
  • the organoaluminum compound the general formula AlRR′R ′′ (wherein R and R ′ are each independently a C 1 to C 10 hydrocarbon group or a hydrogen atom, and R ′′ is C 1 an organoaluminum compound represented by a hydrocarbon group) of ⁇ C 10 are preferred.
  • the organoaluminum compound include trialkylaluminum, dialkylaluminum chloride, alkylaluminum dichloride, and dialkylaluminum hydride. Among these, trialkylaluminum is preferable.
  • examples of the trialkylaluminum include triethylaluminum and triisobutylaluminum.
  • the content of the organoaluminum compound in the polymerization catalyst composition is preferably 1 to 50 times mol, and more preferably about 10 times mol to the metallocene complex.
  • the metallocene complex represented by the general formula (I) and the formula (II) and the half metallocene cation complex represented by the above general formula (III) are each used as an appropriate promoter. By combining them, the amount of cis-1,4 bonds and the molecular weight of the resulting copolymer can be increased.
  • B-1 ionic compound composed of non-coordinating anion and cation
  • aluminoxane (B-2) aluminoxane
  • Lewis acid complex compound of metal halide and Lewis base
  • the polymerization catalyst composition contains at least one of the ionic compound (B-1) and the halogen compound (B-3), the polymerization catalyst composition further comprises: (C) Component: The following general formula (i): YR 1 a R 2 b R 3 c (i) [Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R 1 and R 2 are the same or different and have 1 to 10 carbon atoms.
  • the ionic compound (B-1) and the halogen compound (B-3) do not have a carbon atom to be supplied to the component (A), the above (A) as a carbon supply source to the component (A) Component C) is required.
  • the polymerization catalyst composition contains the aluminoxane (B-2), the polymerization catalyst composition can contain the component (C).
  • the polymerization catalyst composition may contain other components such as a co-catalyst contained in a normal rare earth element compound-based polymerization catalyst composition.
  • the concentration of the component (A) contained in the second polymerization catalyst composition is preferably in the range of 0.1 to 0.0001 mol / l.
  • the component (A) used in the second polymerization catalyst composition is a rare earth element compound or a reaction product of the rare earth element compound and a Lewis base.
  • the reaction of the rare earth element compound and the rare earth element compound with a Lewis base is performed.
  • the object does not have a bond between rare earth element and carbon.
  • the rare earth element compound and the reactant do not have a rare earth element-carbon bond, the compound is stable and easy to handle.
  • the rare earth element compound is a compound containing a lanthanoid element or scandium or yttrium composed of the elements of atomic numbers 57 to 71 in the periodic table.
  • the lanthanoid element examples include lanthanium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.
  • the said (A) component may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the rare earth element compound is preferably a divalent or trivalent salt or complex compound of a rare earth metal, and one or more coordinations selected from a hydrogen atom, a halogen atom and an organic compound residue. More preferably, the rare earth element compound contains a child.
  • reaction product of the rare earth element compound or the rare earth element compound and a Lewis base is represented by the following general formula (XI) or (XII): M 11 X 11 2 ⁇ L 11 w (XI) M 11 X 11 3 ⁇ L 11 w (XII) [Wherein M 11 represents a lanthanoid element, scandium or yttrium, and X 11 independently represents a hydrogen atom, a halogen atom, an alkoxide group, a thiolate group, an amide group, a silyl group, an aldehyde residue, a ketone residue. Represents a group, a carboxylic acid residue, a thiocarboxylic acid residue or a phosphorus compound residue, L 11 represents a Lewis base, and w represents 0 to 3.
  • the group (ligand) bonded to the rare earth element of the rare earth element compound include a hydrogen atom; a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Aliphatic alkoxy groups such as butoxy group; phenoxy group, 2,6-di-tert-butylphenoxy group, 2,6-diisopropylphenoxy group, 2,6-dineopentylphenoxy group, 2-tert-butyl-6- Isopropylphenoxy group, 2-tert-butyl-6-neopentylphenoxy group, 2-isopropyl-6-neopentylphenoxy group; thiomethoxy group, thioethoxy group, thiopropoxy group, thio n-butoxy group, thioisobutoxy group, thio an aliphatic thiolate group such as a sec-
  • aldehyde residues such as salicylaldehyde, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-3-naphthaldehyde; 2′-hydroxyacetophenone, 2′-hydroxybutyrophenone, 2′-hydroxypropiophenone, etc.
  • examples of the Lewis base that reacts with the rare earth element compound include tetrahydrofuran, diethyl ether, dimethylaniline, trimethylphosphine, lithium chloride, neutral olefins, Diolefins and the like.
  • the rare earth element compound reacts with a plurality of Lewis bases (in the formulas (XI) and (XII), when w is 2 or 3), the Lewis base L 11 is the same or different. It may be.
  • Component (B) used in the second polymerization catalyst composition is at least one compound selected from the group consisting of ionic compound (B-1), aluminoxane (B-2), and halogen compound (B-3). is there.
  • the total content of the component (B) in the second polymerization catalyst composition is preferably 0.1 to 50 times mol of the component (A).
  • the ionic compound represented by (B-1) is composed of a non-coordinating anion and a cation, and reacts with the rare earth element compound which is the component (A) or a reaction product thereof with a Lewis base to become cationic.
  • Examples thereof include ionic compounds capable of generating a transition metal compound.
  • non-coordinating anion for example, tetraphenyl borate, tetrakis (monofluorophenyl) borate, tetrakis (difluorophenyl) borate, tetrakis (trifluorophenyl) borate, tetrakis (tetrafluorophenyl) borate, tetrakis ( Pentafluorophenyl) borate, tetrakis (tetrafluoromethylphenyl) borate, tetra (tolyl) borate, tetra (xylyl) borate, (triphenyl, pentafluorophenyl) borate, [tris (pentafluorophenyl), phenyl] borate, tri Decahydride-7,8-dicarbaound decaborate and the like.
  • examples of the cation include a carbonium cation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptatrienyl cation, and a ferrocenium cation having a transition metal.
  • Specific examples of the carbonium cation include trisubstituted carbonium cations such as triphenylcarbonium cation and tri (substituted phenyl) carbonium cation, and more specifically, as tri (substituted phenyl) carbonyl cation, Examples include tri (methylphenyl) carbonium cation, tri (dimethylphenyl) carbonium cation, and the like.
  • ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl) ammonium cation); N, N-dimethylanilinium N, N-dialkylanilinium cation such as cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation; dialkylammonium cation such as diisopropylammonium cation and dicyclohexylammonium cation Is mentioned.
  • trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, and tributylammonium cation (eg, tri (n-butyl)
  • the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tri (methylphenyl) phosphonium cation, and tri (dimethylphenyl) phosphonium cation.
  • the ionic compound is preferably a compound selected and combined from the above-mentioned non-coordinating anions and cations, specifically, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, triphenylcarbohydrate. Preferred is nitrotetrakis (pentafluorophenyl) borate.
  • these ionic compounds can be used individually by 1 type, or 2 or more types can be mixed and used for them.
  • the content of the ionic compound in the second polymerization catalyst composition is preferably 0.1 to 10-fold mol, more preferably about 1-fold mol with respect to component (A).
  • the aluminoxane represented by the above (B-2) is a compound obtained by bringing an organoaluminum compound and a condensing agent into contact with each other.
  • R ′ is a hydrocarbon group having 1 to 10 carbon atoms, and some of the hydrocarbon groups may be substituted with a halogen atom and / or an alkoxy group
  • the degree of polymerization of the unit is preferably 5 or more, and more preferably 10 or more.
  • R ′ examples include a methyl group, an ethyl group, a propyl group, and an isobutyl group, and among these, a methyl group is preferable.
  • organoaluminum compound used as an aluminoxane raw material include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, and mixtures thereof, and trimethylaluminum is particularly preferable.
  • an aluminoxane using a mixture of trimethylaluminum and tributylaluminum as a raw material can be preferably used.
  • the content of the aluminoxane in the second polymerization catalyst composition is such that the element ratio Al / M of the rare earth element M constituting the component (A) and the aluminum element Al of the aluminoxane is about 10 to 1000. It is preferable to do.
  • the halogen compound represented by (B-3) is composed of at least one of a Lewis acid, a complex compound of a metal halide and a Lewis base, and an organic compound containing an active halogen, and is, for example, the component (A).
  • a cationic transition metal compound can be produced by reacting with a rare earth element compound or a reactant thereof with a Lewis base. Note that the total content of halogen compounds in the second polymerization catalyst composition is preferably 1 to 5 moles compared to the component (A).
  • boron-containing halogen compounds such as B (C 6 F 5 ) 3 and aluminum-containing halogen compounds such as Al (C 6 F 5 ) 3 can be used, as well as III, IV,
  • a halogen compound containing an element belonging to the group V, VI or VIII can also be used.
  • aluminum halide or organometallic halide is used.
  • chlorine or bromine is preferable.
  • the Lewis acid examples include methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl aluminum bromide, diethyl Aluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride , Pentachloride , Tin tetrachloride, titanium tetrachloride, tungsten hexachloride, etc., among which diethylaluminum chloride,
  • the metal halide constituting the complex compound of the above metal halide and Lewis base includes beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine.
  • a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, an alcohol, and the like are preferable.
  • tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol, lauryl alcohol are preferred.
  • the Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per mol of the metal halide.
  • the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
  • organic compound containing the active halogen examples include benzyl chloride. .
  • the component (C) used in the second polymerization catalyst composition is represented by the following general formula (i): YR 1 a R 2 b R 3 c (i) [Wherein Y is a metal selected from Group 1, Group 2, Group 12 and Group 13 of the Periodic Table, and R 1 and R 2 are the same or different and have 1 to 10 carbon atoms.
  • R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 may be the same as or different from R 1 or R 2, and Y is a periodic table;
  • a is 1 and b and c are 0, and when Y is a metal selected from Groups 2 and 12 of the Periodic Table, a and b are 1 and c is 0, and when Y is a metal selected from Group 13 of the Periodic Table, a, b and c are 1].
  • organoaluminum compound of the formula (X) examples include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum Hydride, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triis
  • the organometallic compound as the component (C) described above can be used alone or in combination of two or more.
  • the content of the organoaluminum compound in the second polymerization catalyst composition is preferably 1 to 50 times mol, more preferably about 10 times mol for the component (A).
  • the method for producing a copolymer of the present invention includes, for example, (1) the constitution of a polymerization catalyst composition in a polymerization reaction system containing a conjugated diene compound as a monomer and a non-conjugated olefin other than the conjugated diene compound.
  • the components may be provided separately and used as a polymerization catalyst composition in the reaction system, or (2) a previously prepared polymerization catalyst composition may be provided in the polymerization reaction system.
  • (2) includes providing a metallocene complex (active species) activated by a cocatalyst.
  • the amount of the metallocene complex contained in the polymerization catalyst composition is preferably in the range of 0.0001 to 0.01-fold mol with respect to the total of the conjugated diene compound and the non-conjugated olefin other than the conjugated diene compound.
  • the polymerization may be stopped using a polymerization terminator such as ethanol or isopropanol.
  • the polymerization reaction of the conjugated diene compound and the non-conjugated olefin is preferably performed in an atmosphere of an inert gas, preferably nitrogen gas or argon gas.
  • the polymerization temperature of the polymerization reaction is not particularly limited, but is preferably in the range of ⁇ 100 ° C. to 200 ° C., for example, and can be about room temperature. When the polymerization temperature is raised, the cis-1,4 selectivity of the polymerization reaction may be lowered.
  • the pressure for the polymerization reaction is preferably in the range of 0.1 to 10 MPa in order to sufficiently incorporate the conjugated diene compound and the non-conjugated olefin into the polymerization reaction system.
  • the reaction time of the polymerization reaction is not particularly limited, and can be appropriately selected depending on conditions such as the type of monomer to be polymerized, the type of catalyst, and the polymerization temperature.
  • the polymerization time is shorter than the polymerization time for synthesizing a block copolymer of a normal conjugated diene compound and a non-conjugated olefin in order to avoid generation of a long-chain non-conjugated olefin block component.
  • the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol) at the start of the polymerization when the conjugated diene compound and the non-conjugated olefin are polymerized, the concentration of the conjugated diene compound (mol / l) and the concentration of the non-conjugated olefin (mol) at the start of the polymerization.
  • the monomer into the polymerization reaction system can be produced by adjusting the charging method. That is, the second production method of the copolymer of the present invention is characterized in that the chain structure of the copolymer is controlled by controlling the introduction of the conjugated diene compound in the presence of the non-conjugated olefin. Can control the arrangement of monomer units in the copolymer.
  • a polymerization reaction system means the place where superposition
  • the input method of the conjugated diene compound may be either continuous input or split input, and may be a combination of continuous input and split input.
  • continuous injection means adding for a fixed time at a fixed addition rate, for example.
  • the concentration ratio of monomers in the polymerization reaction system can be controlled by dividing or continuously adding the conjugated diene compound to the polymerization reaction system for polymerizing the conjugated diene compound and the non-conjugated olefin.
  • the conjugated diene compound is added, the presence of the non-conjugated olefin in the polymerization reaction system can suppress the formation of a conjugated diene compound homopolymer.
  • the addition of the conjugated diene compound may be performed after the polymerization of the nonconjugated olefin is started.
  • a block copolymer when a block copolymer is produced by the above second production method, it is effective to continuously add a conjugated diene compound in the presence of the nonconjugated olefin to the polymerization reaction system in which the polymerization of the nonconjugated olefin has been started in advance. It becomes.
  • a multi-block copolymer when a multi-block copolymer is produced by the second production method, “a non-conjugated olefin is polymerized in a polymerization reaction system, and then the conjugated diene compound is reacted in the presence of the non-conjugated olefin. It is effective to repeat the operation of “continuous charging into the system” twice or more.
  • the second production method is not particularly limited as described above, except that the method of charging the monomer into the polymerization reaction system as described above.
  • the solution polymerization method, the suspension polymerization method, the liquid phase bulk polymerization method, Any polymerization method such as an emulsion polymerization method, a gas phase polymerization method, and a solid phase polymerization method can be used.
  • the second production method is the same as the first production method, except that the method of charging the monomer into the polymerization reaction system as described above, and the conjugated diene compound as a monomer Non-conjugated olefins can be copolymerized.
  • the injection quantity of a conjugated diene compound and the injection frequency of a conjugated diene compound are not limited thereto.
  • the method for charging the conjugated diene compound is not particularly limited, and examples thereof include continuous charging and divided charging.
  • the number of times of adding the conjugated diene compound is not particularly limited, but a range of 1 to 5 times is preferable. If the conjugated diene compound is charged too many times, it may be difficult to distinguish it from a random copolymer.
  • the non-conjugated olefin is continuously supplied to the polymerization reaction system. Is preferred. Moreover, the supply method of a nonconjugated olefin is not specifically limited.
  • the rubber composition of the present invention is not particularly limited as long as it contains the block copolymer of the present invention, and can be appropriately selected according to the purpose.
  • the rubber component is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the block copolymer natural rubber, various butadiene rubbers, various styrene-butadiene copolymer rubbers, isoprene rubbers of the present invention.
  • a reinforcing filler can be blended with the rubber composition as necessary.
  • the reinforcing filler include carbon black and inorganic filler, and at least one selected from carbon black and inorganic filler is preferable.
  • the inorganic filler is not particularly limited and may be appropriately selected depending on the intended purpose.
  • silica, aluminum hydroxide, clay, alumina, talc, mica, kaolin, glass balloon, glass beads, calcium carbonate examples thereof include magnesium carbonate, magnesium hydroxide, calcium carbonate, magnesium oxide, titanium oxide, potassium titanate, and barium sulfate. These may be used individually by 1 type and may use 2 or more types together.
  • silane coupling agent suitably.
  • the content of the reinforcing filler is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the rubber component. If the content of the reinforcing filler is less than 5 parts by mass, the effect of adding the reinforcing filler may not be seen so much, and if it exceeds 200 parts by mass, the rubber filler is mixed with the reinforcing filler. There is a tendency that it does not get caught, and the performance as a rubber composition may be reduced.
  • ⁇ Crosslinking agent> There is no restriction
  • the content of the crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the rubber component.
  • the content of the cross-linking agent is less than 0.1 parts by mass, the cross-linking hardly proceeds, and when the content exceeds 20 parts by mass, the cross-linking tends to progress during kneading with a part of the cross-linking agent.
  • the physical properties of the sulfide may be impaired.
  • vulcanization accelerators can be used in combination.
  • vulcanization accelerators include guanidine, aldehyde-amine, aldehyde-ammonia, thiazole, sulfenamide, thiourea, thiuram, Dithiocarbamate and xanthate compounds can be used.
  • Known materials such as ultraviolet ray inhibitors, antistatic agents, anti-coloring agents, and other compounding agents can be used depending on the intended use.
  • the crosslinked rubber composition of the present invention is not particularly limited as long as it is obtained by crosslinking the rubber composition of the present invention, and can be appropriately selected according to the purpose.
  • the crosslinking conditions are not particularly limited and may be appropriately selected depending on the intended purpose. However, a temperature of 120 ° C. to 200 ° C. and a heating time of 1 minute to 900 minutes are preferable.
  • the tire of the present invention is not particularly limited as long as the rubber composition of the present invention or the crosslinked rubber composition of the present invention is used, and can be appropriately selected according to the purpose.
  • Examples of the application site in the tire of the rubber composition of the present invention or the crosslinked rubber composition of the present invention include, but are not limited to, a tread, a base tread, a sidewall, a side reinforcing rubber, and a bead filler. .
  • a method for manufacturing the tire a conventional method can be used. For example, on a tire molding drum, members usually used for manufacturing a tire such as a carcass layer, a belt layer, and a tread layer made of unvulcanized rubber are sequentially laminated, and the drum is removed to obtain a green tire. Next, the desired tire can be manufactured by heat vulcanizing the green tire according to a conventional method.
  • the rubber composition of the present invention or the crosslinked rubber composition of the present invention may be used for anti-vibration rubber, seismic isolation rubber, belts (conveyor belts), rubber crawlers, various hoses, Moran and the like. it can.
  • Example 1 After 150 ml of toluene was added to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.4 MPa. On the other hand, in a glove box under a nitrogen atmosphere, bis (2-phenylindenyl) gadolinium bis (dimethylsilyl) amide [(2-PhC 9 H 6 ) 2 GdN (SiHMe 2 ) 2 ] 14.5 ⁇ mol was placed in a glass container.
  • Example 2 After 1 L of toluene was added to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa.
  • Example 3 After 1 L of toluene was added to a sufficiently dry 2 L stainless steel reactor, ethylene was introduced at 0.8 MPa.
  • the ampoule is kept at the aging temperature (25 ° C.), and a toluene solution of 0.0067 mmol of 2-methoxycarbonylmethylcyclopentadienyltrichlorotitanium [MeO (CO) CH 2 CpTiCl 3 ] (TiES) is added dropwise for aging time (5 minutes ) Hold. Thereafter, a solution of 2.0 g of butadiene and 6.0 g of toluene was added at ⁇ 25 ° C., and polymerization was performed at this temperature for 30 minutes. Subsequently, a pressure of 5 kgf / cm 2 was applied to the vessel with ethylene, and the reaction was allowed to proceed for about 1 hour.
  • a toluene solution of 0.0067 mmol of 2-methoxycarbonylmethylcyclopentadienyltrichlorotitanium [MeO (CO) CH 2 CpTiCl 3 ] (TiES) is added dropwise for
  • copolymer E block copolymer
  • FIG. 4 shows the DSC curve of copolymer D.
  • FIG. 5 shows a DSC curve of copolymer E, and
  • FIG. 6 shows a DSC curve of copolymer F.
  • shaft of a DSC curve shows a heat flow rate.
  • FIG. DSC curve of the copolymer D of 4 in a temperature range of 40 ° C. ⁇ 140 ° C., a peak derived from a block portion composed of monomer units of ethylene is not clearly observed, also copolymers F 13
  • the peak derived from ethylene at 27.5 ppm to 33 ppm many peaks other than the peak at 29.4 ppm showing ethylene of 4 chains or more (indicating a block part) are observed, and ethylene is 3 chains or less
  • ethylene is 3 chains or less
  • the endothermic peak at 110 ° C or higher derived from the above random parts in which butadiene and ethylene monomer units (including low molecular weight blocks) are randomly arranged, and short block parts consisting of ethylene monomer units A broad endothermic peak was observed at 40 ° C. to 110 ° C., indicating the formation of.
  • the peak area at 70 ° C. to 110 ° C. is 60% or more of the peak area at 40 ° C. to 140 ° C. and 110 ° C.
  • Examples 1 to 3 using a block copolymer having a peak area at 140 ° C. of 20% or less of a peak area at 40 ° C. to 140 ° C. are more than Comparative Examples 1 to 5 using no block copolymer. It can be seen that it is excellent in terms of fatigue resistance, low exothermic property, and fracture elongation.
  • the copolymer of the present invention can be used for elastomer products in general, particularly for tire members.

Abstract

Cette invention concerne un copolymère séquencé comprenant un composé diène conjugué et une oléfine non conjuguée, une composition de caoutchouc contenant ledit copolymère séquencé, une composition de caoutchouc réticulée obtenue par réticulation de la composition de caoutchouc, et un pneu utilisant ladite composition de caoutchouc ou composition de caoutchouc réticulée. Dans une analyse calorimétrique différentielle (ACD) selon la norme JIS K 7121-1987, la surface de pic à 70-110oC du copolymère précité, qui est un copolymère d'un composé diène conjugué et d'une oléfine non conjuguée et qui est un copolymère séquencé, correspond à 60 % ou plus de sa surface de pic à 40-140oC et sa surface de pic à 110-140oC correspond à 20 % ou moins de sa surface de pic à 40-140oC.
PCT/JP2012/003507 2011-06-02 2012-05-29 Copolymère, composition de caoutchouc, composition de caoutchouc réticulée, et pneu WO2012164914A1 (fr)

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BR112013030818A BR112013030818A2 (pt) 2011-06-02 2012-05-29 copolímero, composição de borracha, composição de borracha reticulada e pneu
CN201280026894.0A CN103562246B (zh) 2011-06-02 2012-05-29 共聚物、橡胶组合物、交联橡胶组合物和轮胎
RU2013156826/04A RU2553474C1 (ru) 2011-06-02 2012-05-29 Сополимер, резиновая смесь, сшитая резиновая смесь и шина
JP2013517875A JP5739991B2 (ja) 2011-06-02 2012-05-29 共重合体、ゴム組成物、架橋ゴム組成物、及びタイヤ
EP12793513.8A EP2716670B1 (fr) 2011-06-02 2012-05-29 Copolymère, composition de caoutchouc, composition de caoutchouc réticulée, et pneu
US14/119,915 US9139680B2 (en) 2011-06-02 2012-05-29 Copolymer, rubber composition, crosslinked rubber composition, and tire

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WO2019171679A1 (fr) * 2018-03-05 2019-09-12 株式会社ブリヂストン Copolymère, procédé de production d'un copolymère, composition de caoutchouc et pneumatique
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CN108690167B (zh) 2017-04-11 2021-07-23 中国科学院长春应用化学研究所 一种乙烯与共轭二烯的共聚物及其制备方法
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JP2015212333A (ja) * 2014-05-02 2015-11-26 株式会社ブリヂストン マルチブロック共重合体、ゴム組成物及びタイヤ
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JPWO2019097853A1 (ja) * 2017-11-16 2020-12-03 株式会社ブリヂストン 共重合体、共重合体の製造方法、ゴム組成物及びタイヤ
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WO2024088247A1 (fr) * 2022-10-24 2024-05-02 中国石油化工股份有限公司 Copolymère, son procédé de préparation, caoutchouc vulcanisé et son utilisation

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RU2553474C1 (ru) 2015-06-20
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CN103562246B (zh) 2015-07-15
US9139680B2 (en) 2015-09-22
JP5739991B2 (ja) 2015-06-24
BR112013030818A2 (pt) 2016-12-06
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EP2716670B1 (fr) 2017-01-18
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